CN103958573B - Polysiloxane-polycarbonate copolymer and manufacture method thereof - Google Patents
Polysiloxane-polycarbonate copolymer and manufacture method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
- C08G77/52—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages containing aromatic rings
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Abstract
The present invention relates to polysiloxane-polycarbonate copolymer and manufacture method thereof. More specifically, the present invention relates to polysiloxane-polycarbonate copolymer, the molecular weight that wherein forms the siloxanyl monomers of this copolymer maintains extra high level and therefore in the situation that of low content of siloxane even, can realize good low-temperature impact resistance, and the viscosity that maintains copolymer is in low level with therefore can improve mobility and mouldability; With the manufacture method that relates to polysiloxane-polycarbonate copolymer.
Description
Technical field
The present invention relates to polysiloxane-polycarbonate copolymer and manufacture method thereof. More specifically,The present invention relates to polysiloxane-polycarbonate copolymer, wherein form the siloxanes list of this copolymerThe molecular weight of body maintains extra high level and therefore in the situation of even low content of siloxaneUnder, can realize good low-temperature impact resistance, and the viscosity that maintains copolymer in low level andTherefore can improve mobility and mouldability; With the system that relates to polysiloxane-polycarbonate copolymerMaking method.
Background technology
Merlon has good mechanical performance, for example hot strength, and impact resistance, etc.,And also there is good dimensional stability, heat resistance and optical clarity. Therefore, it is by extensiveGround is for much industry. But, although Merlon at room temperature has good shock resistanceProperty, but its impact resistance becomes grain at low temperatures fast.
In order to improve this shortcoming, study various polymer, and known polysiloxanes-poly-carbonic acidEster copolymer has relatively good low-temperature impact resistance. But, the polysiloxanes of use at present-Copolycarbonate requires the siloxanes of high-load routinely, to show low-temperature impact resistance,Therefore manufacturing cost must increase. In addition, their problem be mobility and mouldability because ofThe increase of this molecular weight of copolymer and deteriorated.
Therefore, need to develop polysiloxane-polycarbonate copolymer, it can demonstrate low temperature anti-impactHitting property, is even adopting low content of siloxane in the situation that, have simultaneously improved mobility andMouldability.
[prior art document]
<patent documentation>
US2003/0105226A
Disclosure of the invention
Technical problem
The problem that quasi-solution of the present invention certainly involves in above-described prior art. Skill of the present inventionArt object is to provide in the situation that even adopting low content of siloxane, demonstrates good low temperatureImpact resistance has the polysiloxane-polycarbonate of improved mobility and mouldability altogether simultaneouslyPolymers.
The solution of this problem
The invention provides a kind of polysiloxane-polycarbonate copolymer, it comprises following chemical formulaThe hydroxy-end capped siloxanes of 1a or Chemical formula 1 and the Merlon block of following chemical formula 4 are doneFor repetitive, wherein the number-average molecular weight of hydroxy-end capped siloxanes is 2,500 to 15,000:
[Chemical formula 1 a]
[Chemical formula 1]
In another aspect, the invention provides the side of preparing polysiloxane-polycarbonate copolymerMethod, the method comprises that mixed number average molecular weight is 2,500 to 15,000 hydroxy-end capped silicaThe step of alkane and oligomeric Merlon; Make hydroxy-end capped siloxanes and oligomeric MerlonUnder interfacial reaction conditions, reaction is to form the step of polysiloxane-polycarbonate intermediate; With logicalCross the step that uses first this intermediate of polymerization catalyst polymerization.
The beneficial effect of the invention
By comprising the siloxanes with the control molecular weight (or length) in special high-load,Can effectively demonstrate low temperature impact according to polysiloxane-polycarbonate copolymer of the present inventionProperty, this can not show in the time that content of siloxane is low, and under the viscosity average molecular weigh of this copolymerFall, thereby cause the improvement of mobility in extrusion molding/injection moulding and cool time to reduce. In addition, systemCause originally and can decline with ensureing that the required siloxanes amount of low-temperature impact resistance reduces.
Invention pattern
Below, the present invention will more specifically be described. By following embodiment, of the present inventionObject, feature and advantage will readily appreciate that. The embodiment that the invention is not restricted to explain herein,And can in other forms, manifest. Provide the embodiment of introducing herein, in order that make disclosedContent thoroughly and comprehensively, and convey to fully those skilled in the art's spirit of the present invention.Therefore, the invention is not restricted to following embodiment and embodiment.
Term as used herein " product " refers to by making two or more reactants anti-The material of answering and form.
In addition, although for polymerization catalyst is described, used term " first " herein, " second "Deng, but polymerization catalyst is not limited by these terms. These terms are only poly-for distinguishing each otherClose catalyst. For example, the first polymerization catalyst and the second polymerization catalyst can have identical typeCatalyst or different types of catalyst.
In addition, in chemical formula described herein, although for representing hydrogen, halogen atom and/Or the English character " R " of alkyl etc. has numerical value subscript, but " R " do not limited by this subscript." R " represents hydrogen independently, halogen atom and/or alkyl etc. For example, though two or more" R " has identical numerical value subscript, but this " R " can represent identical alkyl or different alkyl. ThisOutward, even if two or more " R " have different numerical value subscripts, but this " R " can represent phaseWith alkyl or different alkyl.
[polysiloxane-polycarbonate copolymer (Si-PC)]
Polysiloxane-polycarbonate copolymer of the present invention comprises following Chemical formula 1 a or chemical formula1 hydroxy-end capped siloxanes and the Merlon block of following chemical formula 4 are as repetitive.
[Chemical formula 1 a]
In above-mentioned Chemical formula 1 a,
R1Represent independently hydrogen atom, halogen atom, hydroxyl, or there is 1-20 carbon atomAlkyl, alkoxyl or aryl. For example, halogen atom can be Cl or Br, and alkyl canThe alkyl with 1-13 carbon atom, for example, methyl, ethyl or propyl group. In addition, for example,Alkoxyl can be the alkoxyl with 1-13 carbon atom, for example methoxyl group, ethyoxyl or thirdOxygen base, and aryl can be the aryl with 6-10 carbon atom, for example phenyl, chlorphenyl orTolyl.
R2Represent to have independently alkyl or the hydroxyl of 1-13 carbon atom. For example, R2CanAlkyl or the alkoxyl with 1-13 carbon atom, have 2-13 carbon atom thiazolinyl orThiazolinyl oxygen base, has cycloalkyl or the cycloalkyloxy of 3-6 carbon atom, has 6-10 carbon formerThe aryloxy group of son, has aralkyl or the aralkoxy of 7-13 carbon atom, or has 7-13The alkaryl of individual carbon atom or aryloxy alkyl.
R3Represent to have independently the alkylidene of 2-8 carbon atom.
Subscript " m " represents integer 0-4 independently.
Subscript " n " represents integer 30-200 independently, preferably 40-170, and more preferably 50-120.
In one embodiment, as the hydroxy-end capped siloxanes of Chemical formula 1 a, can useAvailable from the siloxanyl monomers of DowCorning (
), but be not limited to this.
[Chemical formula 1]
In above-mentioned Chemical formula 1, R1,R2,R3With fixed in the same manner in m and above Chemical formula 1 aJustice, and n represents integer 15-100 independently, preferably 20-80, and more preferably 25-60.
" A " represents the structure of following Chemical formula 2 or 3.
[Chemical formula 2]
In Chemical formula 2,
X represents Y or NH-Y-NH, and wherein Y represents to have the straight chain of 1-20 carbon atomOr the aliphatic group of side chain, cycloalkylidene (for example, thering is the cycloalkylidene of 3-6 carbon atom),Or have 6-30 carbon atom and do not replace or by halogen atom, alkyl, alkoxyl, arylOr the list of carboxyl substituted-or encircle arlydene more. For example, Y does not replace or former by halogenThe aliphatic group that son replaces, includes aerobic at its main chain, the aliphatic group of nitrogen or sulphur atom, orCan be by bisphenol-A, resorcinol, quinhydrones or the derivative arlydene of diphenyl phenol. Y can be for exampleRepresent with one of following Chemical formula 2 a-2h.
[Chemical formula 2 a]
[Chemical formula 2 b]
[Chemical formula 2 c]
[Chemical formula 2 d]
[Chemical formula 2 e]
[Chemical formula 2 f]
[Chemical formula 2 g]
[Chemical formula 2 h]
[chemical formula 3]
In above-mentioned chemical formula 3,
R4Represent to have aromatic hydrocarbyl or the aromatics/aliphatic mixed type alkyl of 6-30 carbon atom,Or there is the aliphatic hydrocarbyl of 1-20 carbon atom. R4Can have halogen-containing, oxygen, nitrogen or sulphurAnd the structure of carbon atom. For example, R4Can be phenyl, chlorphenyl, or tolyl (preferably benzeneBase).
In one embodiment, the hydroxy-end capped siloxanes of Chemical formula 1 can be above-mentionedizationThe hydroxy-end capped siloxanes of formula 1a (wherein n is integer 15-100) and acyl compounds anti-Answer product.
This acyl compounds can for example have aromatic structure, aliphatic structure, or containing aromatics and fatThe hybrid architecture of these two kinds of forms of family. When acyl compounds has aromatic structure or mixed type knotWhen structure, it can have 6-30 carbon atom, and in the time that acyl compounds has aliphatic structure, itCan there is 1-20 carbon atom. Acyl compounds can further comprise halogen, oxygen, and nitrogen or sulphur are formerSon.
In another embodiment, on the hydroxy-end capped siloxanes of above-mentioned Chemical formula 1 can beState hydroxy-end capped siloxanes and the vulcabond of Chemical formula 1 a (wherein n is integer 15-100)The product of compound.
Diisocyanate cpd can be for example Isosorbide-5-Nitrae-phenylene diisocyanate, 1,3-benzene, two isocyanic acidsEster or 4,4'-methylenediphenyl diisocyanates.
In another embodiment, on the hydroxy-end capped siloxanes of above-mentioned Chemical formula 1 can beState hydroxy-end capped siloxanes and the phosphorus-containing compound of Chemical formula 1 a (wherein n is integer 15-100)The product of (for example, aromatics or aliphatic phosphate compound).
Phosphorus-containing compound can have the structure of following Chemical formula 1 b.
[Chemical formula 1 b]
In above-mentioned Chemical formula 1 b, R4As definition in the same manner in above chemical formula 3, and Z is onlyOn the spot represent phosphorus, halogen atom, hydroxyl, carboxyl, alkyl (thering is 1-20 carbon atom), alkaneOxygen base or aryl.
In polysiloxane-polycarbonate copolymer according to the present invention, above-mentioned Chemical formula 1 a orNumber-average molecular weight (the M of the hydroxy-end capped siloxanes of Chemical formula 1n) be 2,500-15,000, preferably3,000-13,000, and more preferably 4,000-9,000. If the number-average molecular weight of siloxanyl monomers is littleIn 2,500,, compared with requirement of the present invention, the effect of improving low-temperature impact resistance may be not enough.If the number-average molecular weight of siloxanyl monomers is greater than 15,000, reactivity may decline, and thereforeIn the synthetic polysiloxane-polycarbonate copolymer with desired molecule amount, have problems.
In polysiloxane-polycarbonate copolymer according to the present invention, comprise as repetitiveMerlon block can represent with following chemical formula 4.
[chemical formula 4]
In above-mentioned chemical formula 4,
R5Represent to have the aromatic hydrocarbyl of 6-30 carbon atom, described aromatic hydrocarbyl do not replace orPerson is had the alkyl (for example, having the alkyl of 1-13 carbon atom) of 1-20 carbon atom, ringAlkyl (for example, having the cycloalkyl of 3-6 carbon atom), thiazolinyl (for example, has 2-13 carbonThe thiazolinyl of atom), alkoxyl (for example, thering is the alkoxyl of 1-13 carbon atom), halogen atomOr nitro replaces.
This aromatic hydrocarbyl can be derived from the compound of following chemical formula 4a.
[chemical formula 4a]
In above-mentioned chemical formula 4a,
X represents alkylidene; Do not there is the straight chain of any functional group, side chain or cyclic alkylidene;Or containing functional group, for example sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, isobutyl phenenylDeng straight chain, side chain or cyclic alkylidene. Preferably, X has 1-10 carbon atomThe alkylidene of straight or branched, or there is the cyclic alkylidene of 3-6 carbon atom.
R6Represent independently hydrogen atom, halogen atom or alkyl, for example, have 1-20 carbon atomStraight or branched alkyl, or there is the cycloalkyl of the individual carbon atom of 3-20 (preferably 3-6).
Subscript " n " and " m " represent integer 0-4 independently.
The compound of above-mentioned chemical formula 4a can be for example two (4-hydroxyphenyl) methane, two (4-oxybenzenesBase) phenylmethane, two (4-hydroxyphenyl) naphthyl methane, two (4-hydroxyphenyl)-(4-isobutyl phenenyl) firstAlkane, two (4-hydroxyphenyl) ethane of 1,1-, 1-ethyl-1, two (4-hydroxyphenyl) propane of 1-, 1-phenyl-1,1-is two(4-hydroxyphenyl) ethane, 1-naphthyl-1, two (4-hydroxyphenyl) ethane of 1-, two (4-hydroxyphenyl) ethane of 1,2-,Two (4-hydroxyphenyl) decane of 1,10-, 2-methyl isophthalic acid, two (4-hydroxyphenyl) propane of 1-, 2,2-two (4-hydroxyphenyl)Propane, two (4-hydroxyphenyl) butane of 2,2-, two (4-hydroxyphenyl) pentanes of 2,2-, 2,2-two (4-hydroxyphenyl) is ownAlkane, two (4-hydroxyphenyl) nonanes of 2,2-, two (3-methyl-4-hydroxyphenyl) propane of 2,2-, two (the fluoro-4-of 3-of 2,2-Hydroxyphenyl) propane, 4-methyl-2, two (4-hydroxyphenyl) pentanes of 2-, two (4-hydroxyphenyl) heptane of 4,4-, hexicholBase-bis-(4-hydroxyphenyl) methane, resorcinol, quinhydrones, 4,4'-dihydroxy phenyl ether [two (4-hydroxyphenyl)Ether], 4,4'-dihydroxy-2,5-dihydroxy diphenyl ether, 4,4'-dihydroxy-3,3'-dichloro-diphenyl ether, two(3,5-dimethyl-4-hydroxyphenyl) ether, two (the chloro-4-hydroxyphenyl of 3,5-bis-) ether, Isosorbide-5-Nitrae-dihydroxy-2,5-Dichloro-benzenes, Isosorbide-5-Nitrae-dihydroxy-3-methylbenzene, 4,4'-dihydroxybiphenyl phenol [p, p'-dihydroxy phenyl],3,3'-bis-is chloro-4,4'-dihydroxy phenyl, two (4-hydroxyphenyl) cyclohexanes of 1,1-, two (3, the 5-dimethyl of 1,1--4-hydroxyphenyl) cyclohexane, two (the chloro-4-hydroxyphenyl of 3, the 5-bis-) cyclohexanes of 1,1-, two (3, the 5-diformazans of 1,1-Base-4-hydroxyphenyl) cyclododecane, two (4-hydroxyphenyl) cyclododecanes of 1,1-, two (4-hydroxyphenyl) fourths of 1,1-Alkane, two (4-hydroxyphenyl) decane of 1,1-, Isosorbide-5-Nitrae-bis-(4-hydroxyphenyl) propane, Isosorbide-5-Nitrae-bis-(4-hydroxyphenyl) butane,Isosorbide-5-Nitrae-bis-(4-hydroxyphenyl) iso-butane, two (4-hydroxyphenyl) butane of 2,2-, 2,2-two (the chloro-4-hydroxyphenyl of 3-)Propane, two (3,5-dimethyl-4-hydroxyphenyl) methane, two (the chloro-4-hydroxyphenyl of 3,5-bis-) methane, 2,2-Two (3,5-dimethyl-4-hydroxyphenyl) propane, two (the bromo-4-hydroxyphenyl of 3, the 5-bis-) propane of 2,2-, 2,2-is two(the chloro-4-hydroxyphenyl of 3,5-bis-) propane, two (4-the hydroxyphenyl)-2-methyl-butane of 2,4-, 4,4'-sulfo-biphenylPhenol [two (4-hydroxyphenyl) sulfone], two (3,5-dimethyl-4-hydroxyphenyl) sulfone, two (the chloro-4-hydroxyphenyl of 3-) sulfone,Two (4-hydroxyphenyl) thioether, two (4-hydroxyphenyl) sulfoxide, two (3-methyl-4-hydroxyphenyl) thioether, two(3,5-dimethyl-4-hydroxyphenyl) thioether, two (the bromo-4-hydroxyphenyl of 3,5-bis-) sulfoxide, 4,4'-dihydroxyBenzophenone, 3,3', 5,5'-tetramethyl-4,4'-dihydroxy benaophenonel, 4,4'-dihydroxybiphenyl, firstBase quinhydrones, 1,5-dihydroxy naphthlene or 2,6-dihydroxy naphthlene, but the invention is not restricted to this. Work as at themIn, representational one is two (4-hydroxyphenyl) propane (bisphenol-A) of 2,2-. About other senses twoUnit's phenols, can be with reference to United States Patent(USP) Nos. 2,999,835; 3,028,365; 3,153,008 He3,334,154. Above-mentioned dihydric phenols can be separately or in conjunction with two or more uses in them.
In carbonate precursor situation, can use for example phosgene (phosgene), carbonyl bromide, two halogenSubtituted acid ester, diphenyl carbonate, dimethyl carbonates etc. are as another monomer of polycarbonate resin.
In polysiloxane-polycarbonate copolymer of the present invention, the use of hydroxy-end capped siloxanesAmount is for 1-10wt%, and more preferably 2-5wt%. If the consumption of hydroxy-end capped siloxanes is less than1wt%,, compared with requirement of the present invention, the effect of improving low-temperature impact resistance may be not enough.If the consumption of hydroxy-end capped siloxanes is greater than 10wt%, physical property, for example mobility,Heat resistance, transparency etc. may be deteriorated, and manufacturing cost may adversely increase. In the present inventionIn, because use has the siloxanyl monomers of relative HMW, therefore, can even adoptLow content of siloxane, for example, under the level of 1-10wt%, demonstrates good low-temperature impact resistance.
Preferably, the viscosity average molecular weigh (M of polysiloxane-polycarbonate copolymerv) be15,000-30,000, and more preferably 17,000-22,000. If the viscosity average molecular weigh of this copolymer is littleIn 15,000, its mechanical performance may be seriously deteriorated. If viscosity average molecular weigh is greater than 30,000,Thereby melt viscosity increases and may exist the problem of process of resin. In the present invention, according toThere is the use of the siloxanyl monomers of high-caliber especially molecular weight, can guarantee that good low temperature is anti-Impact, is less than or equal to 30,000 even if the viscosity average molecular weigh of this copolymer drops to, and entersAnd mouldability under the same conditions becomes better. Therefore, even in extrusion molding/injection moulding processThe temperature of processing temperature while being 30,000 situation lower than viscosity average molecular weigh, also can carry out reposefullyMolding, and and then the cost of energy that can reduce rising temperature and cool time, can expect thusIn Shooting Technique, increase productivity ratio continuously. In addition, it can be mixed with other resins of poor heat stabilityMerge and then can easily develop for various application.
[preparation method of polysiloxane-polycarbonate copolymer]
Can, by following step, prepare polysiloxane-polycarbonate copolymer of the present invention: mixNumber-average molecular weight is 2,500-15,000 hydroxy-end capped siloxanes and oligomeric Merlon (exampleAs, mixed weight is than being 1:99 to 10:90), and they are reacted under interfacial reaction conditions,Form polysiloxane-polycarbonate intermediate; With by use the first polymerization catalyst, polymerization shouldIntermediate.
The oligomeric Merlon using in the preparation of polysiloxane-polycarbonate copolymerViscosity average molecular weigh can be 800-20,000, and more preferably 800-15,000, and most preferably1,000-12,000. If the viscosity average molecular weigh of oligomeric Merlon is less than 800, molecular weight dividesCloth may broaden, and physical property may be deteriorated. If the viscosity average molecular weigh of oligomeric MerlonBe greater than 20,000, reactivity may decline.
In one embodiment, can be by add above-described binary in alkaline aqueous solutionPhenolic compound, makes it to become phenates state, then the phenolic compound under phenates state is addedEnter in the carrene of the phosgene that contains injection for reaction, thereby prepare oligomeric poly-carbonic acidEster. In order to prepare this oligomer, the molar ratio range that preferably maintains phosgene and bis-phenol is about 1:1To 1.5:1, and more preferably 1:1 to 1.2:1, if the mol ratio of phosgene and bis-phenol is less than 1, anti-Answering property may decline. If the mol ratio of phosgene and bis-phenol is greater than 1.5, molecular weight excessively increase andTherefore processability may decline.
Conventionally can in the temperature range of about 15-60 DEG C, form the above-mentioned reaction of oligomer.In order to regulate the pH of reactant mixture, can use alkali metal hydroxide (for example, NaOH).
In one embodiment, the step of formation intermediate comprises the silicon that forms hydroxyl end-blockingThe step of the mixture of oxygen alkane and oligomeric Merlon, wherein this mixture can further comprisePhase transfer catalyst, molecular weight regulator and the second polymerization catalyst. In addition, form intermediateStep can comprise and form the siloxanes of hydroxyl end-blocking and the mixture of oligomeric MerlonStep; With after the reaction of hydroxy-end capped siloxanes and oligomeric Merlon completes, enterRow extracts the step of organic phase from gained mixture, and wherein the step of polymerization intermediate can compriseProvide the first polymerization catalyst to arrive the step in the organic phase of extracting.
Particularly, can be by adding the hydroxy-end capped silica of above-mentioned Chemical formula 1 a or Chemical formula 1Alkane, in the mixture containing the organic phase/water of Merlon, and feeds molecular weight regulator subsequentlyWith catalyst.
As molecular weight regulator, can use to prepare the monomer using in Merlon similarMonofunctional compound. This monofunctional compound can be for example based on phenol, for example, to isopropylBase phenol, p-t-butyl phenol (PTBP), to cumyl phenol, to isooctyl phenol with to the different ninth of the ten Heavenly StemsBase phenol, or the derivative of aliphatic alcohol. Preferably can use p-t-butyl phenol (PTBP).
As catalyst, can use polymerization catalyst and/or phase transfer catalyst. This is polymerization catalyzedAgent can be for example triethylamine (TEA), and phase transfer catalyst can be following chemical formula 5Compound.
[chemical formula 5]
(R7)4Q+X-
In above-mentioned chemical formula 5,
R7The alkyl that represents to have 1-10 carbon atom, Q represents nitrogen, or phosphorus, and X representsHalogen atom or-OR8, wherein R8Represent hydrogen atom, there is the alkyl of 1-18 carbon atom,Or there is the aryl of 6-18 carbon atom.
Particularly, phase transfer catalyst can be for example [CH3(CH2)3]4NX,[CH3(CH2)3]4PX,[CH3(CH2)5]4NX,[CH3(CH2)6]4NX,[CH3(CH2)4]4NX,CH3[CH3(CH2)3]3NX or CH3[CH3(CH2)2]3NX, wherein X represents Cl, Br or-OR8, wherein R8Represent hydrogen atom, there is the alkyl of 1-18 carbon atom or there is 6-18The aryl of carbon atom.
The consumption of phase transfer catalyst is about 0.01-10wt% preferably, and more preferably 0.1-10wt%, the gross weight of the mixture of the siloxanes based on hydroxy-end capped and oligomeric Merlon.If the consumption of phase transfer catalyst is less than 0.01wt%, reactivity may decline. If phase transferThe consumption of catalyst is greater than 10wt%, and precipitation or transparency can occur may be deteriorated.
In one embodiment, after preparing polysiloxane-polycarbonate copolymer, use alkaliThe organic phase that washing disperses in carrene, then separates. Subsequently, acid-soluble with 0.1N saltLiquid washing organic phase, then uses distilled water rinsing 2 times or 3 times. After rinsing completely, perseveranceSurely be adjusted in the concentration of the organic phase of disperseing in carrene, and by 30-100 DEG C, excellentSelect at 60-80 DEG C, use the pure water of constant basis, carry out granulation. If the temperature of pure water is lower than 30 DEG C,Granulation speed is low, and therefore the granulation time may be oversize. If the temperature of pure water exceedes 100 DEG C,May be difficult to obtain the Merlon of even big or small pattern. After completing granulation, preferably existDesciccate 5-10 hour at 100-120 DEG C. More preferably, first at 100-110 DEG C, be dried and produceThing 5-10 hour, then dry 5-10 hour at 110-120 DEG C.
Embodiment and comparative example
Embodiment 1
<prepare hydroxy-end capped siloxanes>
In the 500mL three-neck flask of being furnished with condenser, by 0.4mol monomer (BY16-799,DowCorning) be dissolved in 300ml chloroform, then add wherein 67mL triethylamine(TEA) catalyst. Under backflow gained solution, be added on lentamente wherein through 1 hourThe 0.2mol paraphthaloyl chloride (TCL) dissolving in 1,000mL chloroform, and the gained solution that refluxes12 hours. After reaction completes, from this solution, remove solvent, and product is dissolved in to thirdIn ketone, and wash with hot distilled water. By vacuum oven 24 hours, preparation hasHydroxy-end capped siloxanes (number-average molecular weight, the M of the ester bond of following chemical formula 6n：3,300)。Analyze by H-NMR, confirm that this is synthetic, wherein observe polysiloxanes at 2.6ppm placeThe peak of middle methylene, observes the peak of hydrogen in the phenyl ring of TCL at 8.35ppm place, and6.75-7.35ppm place observes in polysiloxanes the peak of hydrogen in phenyl ring.
[chemical formula 6]
<prepare polysiloxane-polycarbonate copolymer>
Under carrene exists, carry out the interfacial reaction of bisphenol-A photoreactive gas in the aqueous solution,Preparation 400mL viscosity average molecular weigh is approximately 1,000 oligomeric polycarbonate blend, in order to obtainMust this oligomeric polycarbonate blend, mix the chemical formula 6 that 3wt% dissolves in carreneThe hydroxy-end capped siloxanes with ester bond, 1.8mL tetrabutylammonium chloride (TBACl), 2.1gP-t-butyl phenol (PTBP) and 275 μ l triethylamines (TEA, the 15wt% aqueous solution) also react 30Minute. Keep the oligomeric polycarbonate blend having reacted for being separated. Separating respectivelyMutually, only collect organic phase, and mix wherein the aqueous solution of 170g NaOH, 360gCarrene and 300 μ l triethylamines (the 15wt% aqueous solution) also react 2 hours. Be separated itAfter, the organic phase increasing by neutralizing treatment viscosity, and separate. Next, use 0.1N hydrochloric acid solutionWashing gained organic phase, then uses distilled water rinsing 2-3 time. After rinsing completes, pass throughUse the pure water of constant basis, granulation organic phase at 76 DEG C. After completing granulation, first existDesciccate 8 hours at 110 DEG C, then at 120 DEG C 10 hours. Divide by H-NMRAnalyse, confirm the synthetic of this copolymer, wherein observe poly-silicon at 2.6ppm and 2.65ppm placeThe peak of the methylene of oxygen alkane, the peak of hydrogen in phenyl ring in 8.35ppm place observes TCL, andThe peak of hydrogen in phenyl ring in 6.95-7.5ppm place observes polysiloxanes. Measure prepared gatheringThe physical property of siloxanes-Copolycarbonate, and in following table 1, result has been shown.
Embodiment 2
<prepare hydroxy-end capped siloxanes>
In the 100mL three-neck flask of being furnished with condenser, under nitrogen atmosphere, by 0.03molEugenol and 0.015mol dimethyl silicone polymer are dissolved in 50mL chlorobenzene completely, soAfter add wherein 0.00364mmol platinum catalyst (platinum (0)-1,3-divinyl-1,1,3,3-tetra-Methyl disiloxane complex compound). Then reflux gained solution 24 hours, and therefrom remove solvent.Wash this product with distilled water, obtain the hydroxy-end capped siloxanes (M of following chemical formula 7n:8,044)。
[chemical formula 7]
<prepare polysiloxane-polycarbonate copolymer>
Under carrene exists, carry out the interfacial reaction of bisphenol-A photoreactive gas in the aqueous solution,Preparation 400mL viscosity average molecular weigh is approximately 1,000 oligomeric polycarbonate blend. To gainedIn oligomeric polycarbonate blend, mix the chemical formula 7 that 4.5wt% dissolves in carreneThe hydroxy-end capped siloxanes with ester bond, 1.8mL tetrabutylammonium chloride (TBACl), 2.8gP-t-butyl phenol (PTBP) and 275 μ l triethylamines (TEA, the 15wt% aqueous solution) also react 30Minute. Keep the oligomeric polycarbonate blend having reacted for being separated. Separating respectivelyMutually, only collect organic phase, and mix wherein the aqueous solution of 170g NaOH, 360gCarrene and 300 μ l triethylamines (the 15wt% aqueous solution) also react 2 hours. Be separated itAfter, the organic phase increasing by neutralizing treatment viscosity, and separate. Next, use 0.1N hydrochloric acid solutionWashing gained organic phase, then uses distilled water rinsing 2-3 time. After rinsing completes, pass throughUse the pure water of constant basis, granulation organic phase at 76 DEG C. After completing granulation, first existDesciccate 8 hours at 110 DEG C, then at 120 DEG C 10 hours. Divide by H-NMRAnalyse, confirm the synthetic of this copolymer, wherein observe poly-silicon at 2.6ppm and 2.65ppm placeThe peak of the methylene of oxygen alkane, the peak of hydrogen in phenyl ring in 8.35ppm place observes TCL, andThe peak of hydrogen in phenyl ring in 6.95-7.5ppm place observes polysiloxanes. Measure prepared gatheringThe physical property of siloxanes-Copolycarbonate, and in following table 1, result has been shown.
Embodiment 3
By with method identical described in embodiment 2, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxy-end capped siloxanes with ester bond of the following chemical formula 8 of preparation(Mn: 12,141), and use the consumption of 4.5wt%. Measure prepared polysiloxanes-poly-carbonic acidThe physical property of ester copolymer, and in following table 1, result has been shown.
[chemical formula 8]
Embodiment 4
By with method identical described in embodiment 2, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxy-end capped siloxanes with ester bond of the following chemical formula 9 of preparation(Mn: 7,000), and use the consumption of 4.5wt%, and use 2.6g p-t-butyl phenol (PTBP).Measure the physical property of prepared polysiloxane-polycarbonate copolymer, and show in following table 1Go out result.
[chemical formula 9]
Embodiment 5
<prepare hydroxy-end capped siloxanes>
Under nitrogen atmosphere, 0.0666mol monomer (BY16-752, DowCorning) is dissolvedIn 100mL benzene, then add wherein 6.66mmol1,4-diazabicyclo [2,2,2]-XinAlkane. Under backflow gained solution, be added on lentamente in 200mL benzene wherein molten through 1 hourThe 0.0333mol4 separating, 4-di-2-ethylhexylphosphine oxide (phenyl isocyanate). After reaction completes, from instituteObtain in solution and remove solvent, and product is dissolved in acetone, then with hot distilled water washing.By vacuum oven 24 hours, prepare the carbamic acid that has of following Chemical formula 10Hydroxy-end capped siloxanes (the M of ester bondn: 6,274). Analyze by H-NMR, confirm that this altogetherPolymers synthetic, wherein 2.75ppm place observe with following Chemical formula 10 in phenyl endThe peak of the hydrogen of the first bond with carbon in the adjacent aliphatic chain of base.
[Chemical formula 1 0]
<prepare polysiloxane-polycarbonate copolymer>
Under carrene exists, carry out the interfacial reaction of bisphenol-A photoreactive gas in the aqueous solution,Preparation 400mL viscosity average molecular weigh is approximately 1,000 oligomeric polycarbonate blend. To gainedIn oligomeric polycarbonate blend, mix the Chemical formula 10 that 4.5wt% dissolves in carreneThe hydroxy-end capped siloxanes with amino-formate bond, 1.8mL tetrabutylammonium chloride(TBACl), 2.6g p-t-butyl phenol (PTBP) and 275 μ l triethylamine (TEA, 15wt% waterSolution) and react 30 minutes. Keep the oligomeric polycarbonate blend having reacted for phaseSeparate. After separation of phases, only collect organic phase, and mix wherein 170g hydroxideThe aqueous solution of sodium, 370g carrene and 300 μ l triethylamines (the 15wt% aqueous solution) also react 2Hour. After being separated, the organic phase increasing by neutralizing treatment viscosity, and separate. Next,By 0.1N hydrochloric acid solution washing gained organic phase, then use distilled water rinsing 2-3 time. In rinsingAfter completing, by using the pure water of constant basis, granulation organic phase at 76 DEG C. Complete grainAfter change, first desciccate 8 hours at 110 DEG C, then at 120 DEG C 10 hours.Analyze by H-NMR, confirm the synthetic of this copolymer, wherein observe at 2.65ppm placeThe peak of the methylene of polysiloxanes, and in 7.1-7.5ppm place observes polysiloxanes in phenyl ringThe peak of hydrogen. Measure the physical property of prepared polysiloxane-polycarbonate copolymer, and underResult has been shown in table 1.
Embodiment 6
<prepare hydroxy-end capped siloxanes>
In the 500mL three-neck flask of being furnished with condenser, under nitrogen atmosphere, by 0.01molPMS-25 (DamiPolychem) is dissolved in 100mL toluene, then adds wherein0.01mol triethylamine (TEA) catalyst. Under backflow gained solution, through 1 hour lentamenteAdd wherein 0.005mol phenylphosphonic dichloride, and the gained solution 5 hours of refluxing. InsteadAfter should completing, from gained solution, remove toluene solvant, and at this product of vacuum ovenThing 24 hours, obtains the hydroxy-end capped siloxanes (M of the phosphate ester-containing of following Chemical formula 11n:5,500)。
[Chemical formula 1 1]
<prepare polysiloxane-polycarbonate copolymer>
Under carrene exists, carry out the interfacial reaction of bisphenol-A photoreactive gas in the aqueous solution,Preparation 400mL viscosity average molecular weigh is approximately 1,000 oligomeric polycarbonate blend. From madeIn standby oligomeric polycarbonate blend, collect organic phase, and mix wherein 4.5wt% twoThe hydroxy-end capped siloxanes of the phosphate ester-containing of the Chemical formula 11 dissolving in chloromethanes, 1.8mL tetra-Butyl ammonium chloride (TBACl), 2.6g p-t-butyl phenol (PTBP) and 275 μ l triethylamines (TEA,The 15wt% aqueous solution) and react 30 minutes. Keep the oligomeric Merlon having reacted to mixThing is for being separated. After separation of phases, only collect organic phase, and mix wherein 170gThe aqueous solution of NaOH, 370g carrene and 300 μ l triethylamines (the 15wt% aqueous solution) are alsoReact 2 hours. After being separated, the organic phase increasing by neutralizing treatment viscosity, and separate.Next,, by 0.1N hydrochloric acid solution washing gained organic phase, then use distilled water rinsing 2-3 time.After rinsing completes, by using the pure water of constant basis, granulation organic phase at 76 DEG C. ?After completing granulation, first desciccate 8 hours at 110 DEG C, then at 120 DEG C 10Hour. Measure the physical property of prepared polysiloxane-polycarbonate copolymer, and in following tableResult has been shown in 1.
Embodiment 7
By with method identical described in embodiment 1, prepare polysiloxane-polycarbonate copolymerizationThing, difference is that to use consumption be 4.5wt% hydroxy-end capped siloxanes (BY16-752,DowCorning,Mn: 3,000). Measure prepared polysiloxane-polycarbonate copolymerPhysical property, and in following table 1, result has been shown.
Comparative example 1
Measure linear Merlon (3022PJ, Mv: 21,000, SamyangCorporation)Physical property, and in following table 1, result has been shown.
Comparative example 2
] measure linear Merlon (3030PJ, Mv:31,200,SamyangCorporation)Physical property, and in following table 1, result has been shown.
Comparative example 3
The physical property of the linear polycarbonate that the viscosity average molecular weigh of measuring synthesized is 70,800,And in following table 1, result is shown.
Comparative example 4
By with method identical described in embodiment 2, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxy-end capped siloxanes with ester bond of the following Chemical formula 12 of preparation(Mn: 1,500) and use the consumption of 4.5wt%, and use 1.5g p-t-butyl phenol (PTBP).Measure the physical property of prepared polysiloxane-polycarbonate copolymer, and show in following table 1Go out result.
[Chemical formula 1 2]
Comparative example 5
By with method identical described in embodiment 4, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxy-end capped siloxanes with ester bond of the following Chemical formula 13 of preparation(Mn: 2,108) and use the consumption of 4.5wt%. Measure prepared polysiloxane-polycarbonateThe physical property of copolymer, and in following table 1, result has been shown.
[Chemical formula 1 3]
Comparative example 6
By with method identical described in embodiment 5, prepare polysiloxane-polycarbonate copolymerizationThing, difference be the following Chemical formula 14 of preparation there is the hydroxy-end capped of amino-formate bondSiloxanes (Mn: Isosorbide-5-Nitrae 27) and use the consumption of 4.5wt%. Measure prepared polysiloxanes-poly-The physical property of carbonate copolymer, and in following table 1, result has been shown.
[Chemical formula 1 4]
Comparative example 7
By with method identical described in embodiment 6, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxy-end capped siloxanes of the phosphate ester-containing of the following Chemical formula 15 of preparation(Mn: 1,300) and use the consumption of 4.5wt%. Measure prepared polysiloxane-polycarbonateThe physical property of copolymer, and in following table 1, result has been shown.
[Chemical formula 1 5]
Comparative example 8
By with method identical described in embodiment 1, prepare polysiloxane-polycarbonate copolymerizationThing, difference is that to use consumption be 4.5wt% hydroxy-end capped siloxanes (BY16-799,DowCorning,Mn: 1,500). Measure prepared polysiloxane-polycarbonate copolymerPhysical property, and in following table 1, result has been shown.
Comparative example 9
By with method identical described in embodiment 2, prepare polysiloxane-polycarbonate copolymerizationThing, difference is the hydroxyl with ester bond that uses the following Chemical formula 16 that consumption is 4.5wt%Siloxanes (the M of base end-blockingn: 17,158). Measure prepared polysiloxane-polycarbonate copolymerizationThe physical property of thing, and in following table 1, result has been shown.
[Chemical formula 1 6]
Table 1
[table 1]
[table 1] (Continued)
As shown in Table 1, with the polysiloxane-polycarbonate copolymer of preparing according to comparative exampleThe respective performances of (or the linear polycarbonate using in comparative example) is compared, according to enforcementThe polysiloxane-polycarbonate copolymer of example preparation demonstrates excellent low-temperature impact resistance conventionally(being more than or equal to 40kgcm/cm) and extension are than (ductilityratio) (being more than or equal to 80%).For example, the copolymer of embodiment 1 has sticky divide equally more much smaller than the Merlon of comparative example 3Son amount, and there is the viscosity average molecular weigh less than the copolymer of comparative example 4 and few content of siloxane,But it demonstrates larger low-temperature impact resistance, extension ratio, and M.I. value. In addition, embodiment1 copolymer has the content of siloxane fewer than the copolymer of comparative example 5, but it demonstratesLarge low-temperature impact resistance and the ratio that extends.
The method of the above-mentioned performance of measurement using in embodiment and comparative example is as described below.
(a) H-NMR (nuclear magnetic resonance spectroscopy): by using AvanceDRX300(Bruker), carry out this analysis.
(b) viscosity average molecular weigh (Mv): by using UbbelohdeViscometer, at 20 DEG CUnder, the viscosity of measurement dichloromethane solution, and according to following equation, estimated performance viscosity [η].
[η]＝1.23x10-5Mv0.83
(c) impact strength: by using impact tester (RESILIMPACTOR, CEASTCo., Ltd.), at room temperature and-50 DEG C, measure impact strength.
(d) at-50 DEG C, the extension of measuring under impact load is than (amount of deflection ratio): according to following etc.Formula, calculates the ratio that extends.
The extensibility * 100% of the extensibility/all samples of extension ratio=sample
(e) melt index (MI) (M.I.): melt index (MI) is illustrated in the mobility under a certain temperature and load,And according to ASTMD1238, at 300 DEG C, under the load of 1.2kgf, measure.
With reference to specific embodiment, the present invention is described. It will be understood by those skilled in the art that conductModified form in the scope that does not depart from essential characteristic of the present invention can realize the present invention. CauseThis, must be aspect they schematic, instead of describe institute in aspect they restrictedDisclosed embodiment. In aforementioned explanation, do not show scope of the present invention, but in appended powerProfit shows scope of the present invention in requiring, and all difference in the scope of equal value with it shouldBe interpreted as being included in the present invention.
Claims (4)
1. a polysiloxane-polycarbonate copolymer, it comprises following Chemical formula 1 a or chemistryThe hydroxy-end capped siloxanes of formula 1 and the Merlon block of following chemical formula 4 are single as repeatingUnit, the wherein number-average molecular weight (M of hydroxy-end capped siloxanesn) be 2500-15000; And poly-siliconViscosity average molecular weigh (the M of oxygen alkane-Copolycarbonatev) be 15000-25000:
[Chemical formula 1 a]
Wherein, in Chemical formula 1 a,
R1Represent independently hydrogen atom, halogen atom, hydroxyl, or there is 1-20 carbon atomAlkyl, alkoxyl or aryl;
R2Represent to have independently alkyl or the hydroxyl of 1-13 carbon atom;
R3Represent to have independently the alkylidene of 2-8 carbon atom;
M represents integer 0-4 independently; And
N represents integer 30-200;
[Chemical formula 1]
Wherein, in Chemical formula 1,
R1Represent independently hydrogen atom, halogen atom, hydroxyl, or there is 1-20 carbon atomAlkyl, alkoxyl or aryl;
R2Represent to have independently alkyl or the hydroxyl of 1-13 carbon atom;
R3Represent to have independently the alkylidene of 2-8 carbon atom;
M represents integer 0-4 independently;
N represents integer 15-100 independently; And
A represents the structure of following formula Chemical formula 2 or 3;
[Chemical formula 2]
Wherein, in Chemical formula 2,
X is Y or NH-Y-NH, wherein Y represent to have 1-20 carbon atom straight chain orThe aliphatic group of side chain, cycloalkylidene, or have 6-30 carbon atom and do not replace or by halogenThe list of element atom, alkyl, alkoxyl, aryl or carboxyl substituted-or encircle arlydene more;
[chemical formula 3]
Wherein, in above-mentioned chemical formula 3,
R4Represent to have aromatic hydrocarbyl or the aromatics/aliphatic mixed type alkyl of 6-30 carbon atom,Or there is the aliphatic hydrocarbyl of 1-20 carbon atom;
[chemical formula 4]
Wherein, in chemical formula 4,
R5Represent to have the aromatic hydrocarbyl of 6-30 carbon atom, described aromatic hydrocarbyl do not replace orPerson is replaced by alkyl, cycloalkyl, thiazolinyl, alkoxyl, halogen atom or nitro.
2. the polysiloxane-polycarbonate copolymer of claim 1, wherein at polysiloxanes-poly-The content of the hydroxy-end capped siloxanes in carbonate copolymer is 1-10wt%.
3. the preparation method of the polysiloxane-polycarbonate copolymer of claim 1 or 2, shouldMethod comprises:
Mixed number average molecular weight is 2500 to 15000 hydroxy-end capped siloxanes and oligomericMerlon also makes them under interfacial reaction conditions, react to form polysiloxane-polycarbonateThe step of intermediate; With
By using the step of first this intermediate of polymerization catalyst polymerization, to obtain sticky equal moleculeAmount (Mv) be the polysiloxane-polycarbonate copolymer of 15000-25000.
4. the preparation method of the polysiloxane-polycarbonate copolymer of claim 3 is wherein lowThe viscosity average molecular weigh of poly-Merlon is 800-20000.
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| KR20110112324 | 2011-10-31 | ||
| KR10-2011-0112324 | 2011-10-31 | ||
| PCT/KR2012/008843 WO2013066002A1 (en) | 2011-10-31 | 2012-10-26 | Polysiloxane-polycarbonate copolymer and method of manufacturing the same |
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| EP (1) | EP2773689A1 (en) |
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| KR101492956B1 (en) * | 2011-12-26 | 2015-02-13 | 주식회사 삼양사 | Method of preparing polysiloxane-polycarbonate copolymer |
| KR101675197B1 (en) * | 2013-07-01 | 2016-11-10 | 주식회사 엘지화학 | Polyorganosiloxane and copolycarbonate resin |
| KR102277384B1 (en) | 2013-10-08 | 2021-07-14 | 코베스트로 도이칠란트 아게 | Preparation of siloxane-containing block copolycarbonates by means of reactive extrusion |
| KR102217411B1 (en) * | 2013-12-10 | 2021-02-19 | 이데미쓰 고산 가부시키가이샤 | Polycarbonate-polyorganosiloxane copolymer and method for producing same |
| KR20160002485A (en) * | 2014-06-30 | 2016-01-08 | 주식회사 삼양사 | Polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance and method for preparing the same |
| KR101779188B1 (en) | 2014-09-05 | 2017-09-15 | 주식회사 엘지화학 | Copolycarbonate and composition comprising the same |
| WO2016036203A1 (en) * | 2014-09-05 | 2016-03-10 | 주식회사 엘지화학 | Copolycarbonate and composition containing same |
| WO2016036202A1 (en) * | 2014-09-05 | 2016-03-10 | 주식회사 엘지화학 | Copolycarbonate and composition comprising same |
| KR101685665B1 (en) | 2014-12-04 | 2016-12-12 | 주식회사 엘지화학 | Copolycarbonate and composition comprising the same |
| KR20160067714A (en) | 2014-12-04 | 2016-06-14 | 주식회사 엘지화학 | Copolycarbonate and article containing the same |
| EP3050908B1 (en) * | 2014-12-04 | 2019-09-04 | LG Chem, Ltd. | Copolycarbonate and composition comprising same |
| KR101948823B1 (en) * | 2015-09-04 | 2019-02-15 | 주식회사 엘지화학 | Novel polyorganosiloxane, and copolycarbonate prepared by using the same |
| KR102030731B1 (en) * | 2015-09-16 | 2019-10-10 | 주식회사 엘지화학 | Novel polyorganosiloxane, and copolycarbonate prepared by using the same |
| WO2017119657A1 (en) * | 2016-01-07 | 2017-07-13 | 주식회사 엘지화학 | Novel polyorganosiloxane and copolycarbonate prepared using same |
| KR101831886B1 (en) * | 2016-01-07 | 2018-04-04 | 주식회사 엘지화학 | Novel polyorganosiloxane, and copolycarbonate prepared by using the same |
| CN106967284B (en) * | 2016-01-14 | 2019-07-30 | 株式会社Lg化学 | Poly carbonate resin composition and the molding being produced from it |
| KR101924199B1 (en) | 2016-02-01 | 2018-11-30 | 주식회사 엘지화학 | Novel polyorganosiloxane, and copolycarbonate prepared by using the same |
| CN105802175B (en) * | 2016-04-08 | 2017-03-15 | 广东优科艾迪高分子材料有限公司 | polyarylate-polydimethylsiloxane block copolymer modified polycarbonate and preparation method thereof |
| KR101828300B1 (en) * | 2016-12-08 | 2018-02-13 | 주식회사 삼양사 | Polycarbonate resin composition having excellent heat resistance and flowability and molded article comprising the same |
| CN107602837A (en) * | 2017-03-17 | 2018-01-19 | 中山市通彩化工科技有限公司 | Polysiloxane polycarbonate random copolymer is used for the purposes for improving plastic alloy intensity |
| US11760841B2 (en) | 2018-12-21 | 2023-09-19 | Dow Silicones Corporation | Silicone-polycarbonate copolymer, sealants comprising same, and related methods |
| WO2020131708A2 (en) | 2018-12-21 | 2020-06-25 | Dow Silicones Corporation | Silicone-organic copolymer, sealants comprising same, and related methods |
| CN111848956B (en) * | 2019-04-30 | 2022-03-11 | 万华化学集团股份有限公司 | Polysiloxane with end group of phenolic group and preparation method thereof |
| KR102383997B1 (en) * | 2020-04-24 | 2022-04-08 | 주식회사 삼양사 | Polysiloxane-polycarbonate copolymer using a mixture of hydroxyl-terminated polysiloxanes and method for preparing the same |
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| US2999835A (en) | 1959-01-02 | 1961-09-12 | Gen Electric | Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same |
| GB1045533A (en) | 1963-02-21 | 1966-10-12 | Gen Electric | Flame-resistant polycarbonate compositions |
| EP0522751B1 (en) | 1991-07-01 | 1998-04-01 | General Electric Company | Polycarbonate-polysiloxane block copolymers |
| JP3703500B2 (en) * | 1992-09-21 | 2005-10-05 | 出光興産株式会社 | Method for producing polycarbonate-polyorganosiloxane copolymer |
| US6630525B2 (en) * | 2001-10-09 | 2003-10-07 | General Electric Company | Polycarbonate-siloxane copolymers |
| US20060030647A1 (en) * | 2004-08-05 | 2006-02-09 | Thomas Ebeling | Flame retardant thermoplastic polycarbonate compositions, use, and method of manufacture thereof |
| US20090088509A1 (en) * | 2007-09-28 | 2009-04-02 | Sabic Innovative Plastics Ip Bv | Copolycarbonate compositions |
| US7994254B2 (en) | 2008-06-20 | 2011-08-09 | Sabic Innovative Plastics Ip B.V. | Polysiloxane-polycarbonate compositions, and related methods and articles |
| KR101145035B1 (en) * | 2009-08-25 | 2012-05-21 | 주식회사 삼양사 | Urethane bond-containing hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer and method of manufacturing the same |
| JP5547953B2 (en) | 2009-12-10 | 2014-07-16 | 出光興産株式会社 | Polycarbonate-polyorganosiloxane copolymer, process for producing the same, and polycarbonate resin containing the copolymer |
| KR101289201B1 (en) | 2010-03-29 | 2013-07-29 | 주식회사 삼양사 | Ester linkage-containing hydroxy-terminated siloxane, polysiloxane-polycarbonate copolymer and method of manufacturing the same |
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| TW201326265A (en) | 2013-07-01 |
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| KR20130047612A (en) | 2013-05-08 |
| US20140249280A1 (en) | 2014-09-04 |
| KR101432677B1 (en) | 2014-08-25 |
| TWI520988B (en) | 2016-02-11 |
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| WO2013066002A1 (en) | 2013-05-10 |
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